Hydroxylated polyamide textile lubricants



v Pcieniet'l Aug. 12, 1947 2,425,393

UNITED STATES PATENT OFFICE HYDROXYLATED POLYAMIDE TEXTILE LUBBICAN TS Edwin ArRobinson, Chatliam, and Maurice J. Kelley, Newark, N. J., assignors to Nopco Chemical Company, Harrison, N. 1., a corporation of New Jersey No Drawing. Application June 23, 1943, Serial No. 491,970

11 Claims. (oi. zoo-404.5)

l 2 This invention relates to textile lubricants and It is a further object of this invention to prosofteners, and more particularly to textile lubrivide a process for the preparation of textile lubricants and softeners comprising mixed fatty polycants and softeners from polyamines. amides. This application is a continuation-in- The foregoing objects are secured and the dispart of our copending application Serial No. advantageous features of the compositions pro- 274,808, filed May 20, 1939, now Patent No. duced in accordance with the prior art are over- 2,345,632. come in polyamides having the general formula:

It. has been proposed to use higher fatty amides 0 R R 0 such as oleic acid amide, oleic acid methyl amide (1) II I II and oleic acid ethylene diamide as softeners and lubricants for textile materials. Such amides are 01 pref y the e pec fi fcrmlllai ordinarily prepared by reacting a fatty acid or 0 R 0 fatty ester with a monoor polyamide. The II I I J I II reaction of monoamines with higher fatty acids (2) R C N N C 'R or fatty esters yields products which are not read- 16 4 i ily dispersible in water and since these products h rei contain no residual amino group they cannot be solubilized to any substantial extent by treatment with acids. Hence, these products cannot be adt m e usly applied to textile material. It has zo represents a fatty acyl radicle containing from been proposed, therefore, to react polyamines 8 to 22 carbon atoms;

with higher fatty acids or fatty esters to produce 0 amides having free amino groups capable of re i II R acting with weak acids so as to solubilize the products and render .them readily dispersible or 25 represents a fatty acy radicle containing frcm I soluble in water. However, the monoamides 1 t0 5 carbon atoms; Z represents an aliphatic f r by such polyammes by reaction thereof linking chain having an unsatisfied valence at with higher fatty acids or fatty esters cause yelbcth ends thereof. Such as aliphatic hydrocarbon lowing of textile material upon application th r radicles; aliphatic hydrocarbon radicles having to and hence are highly unsuitable for use as 80 a yd n o replaced y a ydro y p;

textile lubricants and softeners. On the other d a at yd a n adi les and a iphat hand, polyamides formed by the reaction of highhydrocarbon radicles having a yd atom er fatty acids or fatty esters with polyamines are Placed by a oxyl p, whi radicles y much less desirable as softeners and lubricants be interrupted by one or more eth r, m

than the corresponding monoamides because of trelized c, amido or keto groups; R8 in each we their relatively poor softening and lubricating occurrence. and d p d n y f v y other properties. currence, represents a hydrogen, an alkyl group It has also been proposed to prepare t xtil or an alkylol group, with the proviso that at least lubricants and softeners by reacting unsymmetrione f he Rs bsti uents must e an lkylol cal dialkyl ethylene diamines with higher fatty 0 r up. r a t a iv y, in the case of Formula acids such as oleic acid. Such unsymmetrical 1 the radicle Z y S s y the Proviso y c dialkyl amines are, however, relatively expensive am a hyd xy r up; Ri n a ur and difficult to obtain and hence, while amides and independent y f ev y oth r cur nc pthereof have been used to some extent as textile r sents a hyd en at m or an al y adi and lubricants and softeners, there is a great demand n rep s nts a Sma l W ole numbe in the textile industry for cheaper products which Such hydroxylated pc ye deiiv y be pp may be used in place of these amides. to textile materials, and when so applied impart It is an object of this invention to provide inthereto excellent softness, drape and pliability expensive and highly effective t xtile lubricants without causing yellowing of the material. The and softeners. 6 polyainides Of our invention may be prepared in a simple and inexpensive manner by reacting a readily available hydroxylated polyamine having the general formula:

Ra Rs t. ailgt ialkn under the notation of formulae (1) and (2) supra, with a fatty acid containing from 8 to 22 5 react with the polyamines in accordance with carbon atoms, or an ester or acid halide thereof, and with a short chain fatty acid containing from 2 to 5 carbon atoms. Under the general formulae (1) and (2) it is possible for the polyamides to contain one or more secondary amino groups,

in which case they may be converted to salts by ans of weak acids -to enhance the solubility 'ei'eof. We have found, however, that the presence of substantially more than one secondary amino group in the hvdroxylated polyamides of our invention tends to cause yellowing of any textile material to which the polyamides are applied; hence, if hydroxylated polyamines containing more than 3 nitrogen atoms, e. g., ethanol triethylene tetramine, are employed to prepare the products of our invention, preferably, suflicient amounts of the short chain fatty acids are employed so as to acylate at least all but one of the secondary amino groups. 1

The products of our invention are preferably prepared by reacting a hydroxylated polyamine with a highervfatty acid containin from 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, or an ester thereof so as to form a monoamide, and then reacting the monoamide with suitable amounts of an acid containing from 2 to 5 carbon atoms. However, when employing diamines or triamines in the practice of our invention, the preparation of the amides may be carried out by first reacting the polyamine with the short chain acid and then treating the product with the long chain fatty acid. Any hydroxylated polyamine may be used in the practice of our invention; thus, for example, hydroxylated polyamines such as ethanol ethylene diamine, ethanol diethylene,

triamine, ethanol propylene diamine, symmetrical diethanol ethylene diamine, 1 amino 3 methylamino isopropanol, N ethyl N ethanol ethylene diamine, isopropanol ethylene diamine, 1 amino 2 ethyl 3 ethanol amino isopropanol, l-aminodimethyl 5 methylaminodimethyl n-pentanol-3, 1,3 diamino isopropanol, etc., all coming within the formulae (3) and (4), supra, may be employed. Products of those amines containing 3 or more nitrogen atoms may be converted to salts to enhance the solubility thereof; however, the hydroxyl and short chain acyloxy groups themselves impart a considerable degree of solubility and assist dispersion; accordingly, products prepared from ethanol ethylene diamine have-been found highly satisfactory without conversion to the salt and for this reason, as well as on account of its eheapness, ethanol ethylene diamine is a highly preferred starting material for the synthesis of compositions according to this inven= tion.

The long chain fatty 'eicid compound reacted with the polyamine in accordance with our invention may be any of the fatty acids containing from 8' to 22 carbon atoms, preferably from 12 to 18 carbon atoms, or the esters thereof; the

4 following higher fatty acids may be mentioned by way of examples: caprylic acid, nonylic acid, capric acid, undecylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid,

5 oleic acid, ricinoleic acid, mixtures of these acids, I

etc. In place of the higher fatty acids, derivatives thereof such as glycerides and other esters may be employed. Actually we prefer to use glycerides of the fatty acids since products are 10 obtained having superior softening properties to those resulting from the reaction of the polyamines with the free fatty acids. Products particularly suitable as textile lubricants and softeners are obtained by employing coconut oil to our invention since these products are dispersi-ble in water without further solubilizing treatment and possess excellent lubricating and softening properties. As examples of other glycerides that may be employed in place of the long chain fatty ,acids there may be mentioned teaseed oil, castor oil, hydrogenated castor oil, etc.

The short chain acids employed in accordance with our invention contain from 2 to 5 carbon 25 atoms; thus, for example, acetic acid, glycollic acid, lactic acid, glyceric acid, propionic acid, butyric acid and valeric acid may be employed; derivatives thereof such as esters, acid halides and anhydrides may be employed in-accordance with procedures well known to the art. We prefer to use acetic acid or acetic anhydride in the preparation of our novel products because of their ready availability and the excellent softening properties of the amides prepared from these compounds.

In carrying out the reaction inaccordance with our preferred method, approximately equimolecular quantities of a hydroxylated polyamine and a fatty acid containing from 8 to 22 carbon atoms are mixed; if a glyceride of a fatty acid is employed, e. g., coconut oil, approximately 3 mol of the glyceride per mol of polyamine is used. The compounds are then permitted to react at a temperature sufficiently high to cause the formation of the monoamide; this temperature may vary the particular reactants and somewhat upon the temperature; generally, 8 hours or more are required. The pressure under which the reaction is carried out is preferably atmospheric; however, pressures above or below atmospheric may be employed. The product of the reaction is then mixed with a suitable quantity of a short chain fatty acid containing from 2 to 5 carbonatoms; as above mentioned, anhydrides, esters or "acid halides of these acids may also be employed." The amount of short chain acid compound employed depends to some extent upon the number of amino groups to be acylated and the nature ofthe compound used. Thus, in the case of a triamine such as ethanol diethylene triamine, we prefer to employ g5 about 1 mol of a short chain fatty acid per mol of triamine, leaving 1 amino group free for 'con-. version to the salt; however, in the case of ethanol triethylene tetramine where it is desired to acylate all but one of the secondary amino groups,

' approximately 2 mols of the short chain acid per mol of the polyamine may be employed. It is to be understood that if derivatives of the short chain acid are reacted with the monoamide the amounts thereof will be adjusted accordingly; for w example, approximately one-half mol of acetic anhydride is used where one mol of acetic acid is required. If desired, suiiicient amounts of the short chain acid may be used so that the NH group adjacent to the long chain fatty group may also be acylated. Generally, it may be said that the number of mols of short chain fatty acid employed per mol of polyamine will be equivalent to the number of groups to be acylated in accordance with our invention. The conditions under which this reaction is carried out may vary widely but we have found that the constituents may be reacted at atmospheric pressure and at a temperature of about 135 C. for about 3 to 5 hours, the mixture then raised to between about 150 C. and about 170 C. and the reaction continued for about 5 to about 8 additional hours with excellent results. However, it is to be understood that these conditions may be varied somewhat without affecting the course of the reaction, e. g., pressures above or below atmospheric may be used, the temperatures may vary widely so long as they are sufficiently high to effect acylation and the time of reaction may differ from the time above set forth.

The products of our invention may be liquids or solids, but generally they are solids. The majority of these products are relatively insoluble in water; h'owever, products somewhat soluble or dispersible in water may be obtained. As above mentioned, the coconut oil products are generally dispersible in water. vention contain a free secondary amino group so that they may be treated with weak acids such as acetic acid or lactic acid to solubilize the amides and render them more soluble or dispersible in water. The solubilizing treatment is preferably carried out by mixing a dilute solution of the weak acid with the molten alkylol polyamide, stirring the mixture until it is homogeneous and permitting the mixture to cool. Our novel products may be marketed as such or in the form of an aqueous solution, dispersion or paste thereof. They may be applied to textile material by any of the well known methods, e. 'g., in the form of a dilute solution thereof, and in every case impart excellent softness, drape, flexibility and handle to the textile material.

The following examples are illustrative of our invention. Amounts are given in parts by weight:

EXAMPLE I Coconut oil 679 parts (1 mol) Ethanol ethylene diamine 321 parts (3 mols) Acetic anhyride-.. 181 parts (1 mols) The coconut oil and ethanol ethylene diamine Certain products of our inmaintained for a further 5 hours.

were mixed in an open kettle and agitated at temable as a textile lubricant and softener.

EXAMPLE [I Hydrogenated soyabean oil 67.5 parts (1 mol) Ethanol ethylene diamine 23.0 parts (3 mols) Acetic acid 13.5 parts (3 mols) The hydrogenated soyabean oil and ethanol ethylene diamine were heated together at temperatures in the range 140-150 C. for 6 hours. The acetic acid was then added to the reaction mixagent, particularly in the preparation of textile water-proofing compositions.

EXAMPLE III Stearic acid 284 parts (1 mol) Ethanol ethylene diamine 104 'parts (1 mol) Acetic anhydride 51 parts We mol) The foregoing reactants were condensed together in the same manner as were the corresponding ingredients in Example I. The resultant condensation product was a solid soluble in dilute acid solutions.

EXAMPLE IV Oleic acid 282 parts (1 mol) Ethanol ethylene diamine--- 104 parts (1 mol) Acetic anhydride 51 parts mol) The above ingredients were reacted together exactly as were the corresponding ingredients of Example I. The resultant composition was readily dispersible in aqueous solutions,

EXAMPLE V Refined corn oil 65.5 parts (1 mol) Ethanol ethylene diamine 23.2 parts (3' mols) Acetic anhydride 11.3 parts (1 mols) The corn oil and ethanol ethylene diamine were heated together in a closed kettle at temperatures in the range of -135 C. for 8 hours. At this time an alkali determination conducted upon a sample of the reaction mixture showed 12% of a1- kalinity in the mass, calculated as ethanol ethylene diamine, indicating that approximately onehalf of the amino alkalinity had been blanked off by amidification. The mixture was then cooled to 70 C. and the acetic anhydride slowly added. The temperature was then raised to C. and At the end of this time the acid number of reaction mass was 10. The reaction mixture, when cooled, consisted of a brown colored liquid which was dispersi-ble in water and was capable of producing water-inoil emulsions.

EXAMPLE VI Lauric acid chloride 40 parts (1 mol) Ethanol ethylene diamine 17.5 parts (1 mol) Glyceric acid 12 parts (1 mol) The lauric acid chloride and ethano1 ethylene diamine were agitated together at C. for 7 hours. 0., the glyceric acid was added and the reaction was resumed at 170 C. and continued for 5 additional hours. The resultant condensation product was clearly soluble in water and exhibited excellent lubricating properties. I

EXAMPLE VII Oleic acid 282 parts (1 mol) Ethanol ethylene diamine--- 104 parts (1 mol) Glycollic acid (70% aqueous) 106 parts (1 mol) The oleic acid and ethanol ethylenediamine were agitated together at temperatures-between 150 and 1701 C. for 10 hours and thereafter the mixture was cooled to 120 C. andthe glycollic acid added. The reaction was resumed and continued The resultant product was cooled to 70 7 at 150 0.; for 3 hours. The resultant amide condensation product had outstanding fiber lubricating properties.

Exsurrr VIII 1,3 diamino isopropanol 90 parts (1 mol) Stearic acid 284; parts (1 mol) Acetic anhydride 51 parts (V2 mol) The 1,3 diamino isopropanol and stearic acid were heated together at temperatures ranging 175-200 C. for hours. Thereafter the mixture. was cooled to 70 C., the acetic anhydride added and the temperature again raised to 200 C. for an additional 4 hours.

EXAMPLE DI Textile treatment Cotton sheeting was passed through a quetch containing a aqueous dispersion of the condensation product of Example I. A smooth, soft and even handle resulted on the dried fabric.

EXAMPLE X Parts Paraflin wax (melting point 127 F.) 21 Condensation product produced in accordance with Ex. II 2 Basic aluminum acetate 3 Water 74 The paraflin wax and condensation product were melted together and a solution prepared from the water and aluminum acetate was gradually introduced into the melt with agitation. The

resultant emulsion constituted a stable stock EXAMPLE XI Water-in-oil emulsion Parts Mineral seal oil 22.5 Condensation product of Example III 2.5 Water 75.0

The condensation product and mineral seal oil were dissolved at 45 C. and thereafter the water was heated to 45 C. and slowly introduced into the-melt with steady agitation. The result was a 'water-in-oil (as distinguished from an oil-inwater) emulsion which was suitable for many purposes, for instance, as a base for agricultural sprays, as a lubricant in the molding of ceramic materials, as a defoamer, and for many other Examm x11 Paper tissue softenin Af1% solution of the hydroxy acetic acid salt of the condensation product produced in accordance with Example IV was sprayed onto a tissue paper during the manufacture ther'eof just prior tqits'entry into the calender stack. The paper so produced was softened and flexibilized in a veryfsatisfactory manner. V

Exams: XIII Fat liquor Parts Neats-foot oil 3 Hydroxy acetic acid solution of the condensation product produced in accordance with Example V Water The foregoing constituents were emulsified together and formed a highly satisfactory fat liquor which was used in lubricating alum tanned kid leather. The leather'so treatedwas characterized by highly satisfactory softness and flexibility.

From the foregoing discussion and examples it will be seen that this invention provides novel and excellent polyamide textile lubricants and softeners. The polyamides of this invention 1mpart to the textile material treated therewith a high degree of softness, drape, flexibility and handle, but do not cause any appreciable yellowing of the material even after prolonged contact therewith. The products of our invention have been found to give a softer finish when applied, to textiles than the fatty amides of unsymmetrical dialkyl diamines hereinabove referred to; hence, smaller amounts of our products may be used to soften textiles than are necessary when the latter amides are employed. Furthermore, our products cause less discoloration of the textile material to which they are applied than do the amides of unsymmetrical dialkyl diamines. In addition, the products of our invention are much easier to use than the amides of the unsymmetrical dialkyl diamines since they may be dispersed or dissolved-in water with great ease in contrast to the difiiculties encountered in dispersing or dissolving the latter amides. As above pointed out, our novel products may be prepared from readily available and inexpensive amines and hence are much cheaper than the fatty amides of the unsymmetrical dialkyl diamines.

Therefore, in view of the above, it is evident that the products of this invention display a marked superiority over lubricants and softeners heretothe spinnerettes and may be used as defoam'ing' agents, assistants in dyeing, printing and otherwise treating textiles and the like, and for the preparation of detergents, and wetting, dispersing and emulsifying agents.

wherein R1- -CO represents a fatty acyl radicle' containing from 8 to 22 carbon atoms; OCR:

represents a fatty acyl radicle containing from 2 to 5 carbon atoms; Z represents'an aliphatic linking vradicle having an unsatisfied valence at both ends thereof chosen from the class consist- I, groups, aliphatic acyl groups and alkylol groups;

withthe proviso that at least one of the substituents R3 and Z must contain a hydroxyl group.

2. Alkylol polyamides having the general formula:

wherein R1--CO represents a fatty acyl radicle containing from 8 to 22 carbon atoms; OC-Rz represents a fatty acyl radicle containing from 2 to carbon atoms; R3 in each occurrence, and independently of any other occurrence, represents a substituent chosen from the group consisting of hydrogen, alkyl. groups, aliphatic acyl groups and alkylol groups, with the proviso that at least one of the R3 substituents must be an alkylol group; R4 in each occurrence, and independently of any other occurrence, represents a substituent chosen from the group consisting of hydrogen and alkyl groups; and n represents a small whole number from one to three, inclusive.

3. Alkylol polyamides having the general formula:

wherein Ri-CO- represents a fatty acyl radicle containing from 12 to 18 carbon atoms; OC-Rz represents a fatty acyl radicle containing from 2 to 5 carbon atoms; Rs in each occurrence, and independently of any other occurrence, represents a substituent chosen from the group consisting of hydrogen, alkyl groups, aliphatic acyl groups and alkylol groups, with the proviso that at least one of the R3 substituents must be an alkylol group; R4 in each occurrence, and independently of any other occurrence, representsa substituent chosen from the group consisting of hydrogen and alkyl groups; and n represents a small whole number from one to three, inclusive.

4. Alkylol polyamides having the general formula:

wherein R1--CO- represents the fatty acyl radicles contained. in a fatty glyceride oil; OCR2 represents a fatty acyl radicle containing from 2 to 5 carbon atoms; Rs in each occurrence, and independently of any other occurrence, represents a substituent chosen from the group consisting of hydrogen, alkyl groups, aliphatic acyl groups and alkylol groups, with the proviso that at least one of the Rs substituents must be an alkylol group; R4 in each occurrence, and independently of any other occurrence, represents a substituent chosen from the grou consisting of hydrogen and alkyl groups; and n represents a small whole number from one to three,

inclusive.

5. Alkylol polyamides having the general formula:

H H H R: Recon-(airman, 1k 1!! Q n wherein R1CO represents a fatty acyl radicle containing from 8 to 22 carbon atoms OC--Ra represents a fatty acyl radicle containing from 2 to 5 carbon atoms R: in each occurrence, and independently of any other occurrence, represents a substituent chosen from the group consisting of hydrogen atoms, alkyl groups, aliphatic acyl groups. and alkylol groups, with the proviso that at least one Ra substituent must be an alkylol group; and n represents a small whole number from one to three, inclusive.

6. Alkylol dlamides having the general formula:

wherein R1-CO represents a fatty acyl radicle containing from 8 to 22 carbon atoms; -COR2 represents a fatty acyl radicle containing from 2 to 5 carbon atoms; and Rs in each occurrence. and independently of its other occurrence, represents a substituent selected from the group consisting of hydrogen atoms, .alkyl groups, aliphatic acyl groups and alkylol groups, with the proviso that at least one of the R3 substituents must be an alkylol group.

7. A diamide having the formula:

- H n Hi t-OH n H H wherein Rl-CO represents the fatty acyl radicles contained in coconut oil.

8. A polyamide having the formula:

H-fJ Z-o H H n wherein Ri CO represents the fatty acyl radicles contained in hydrogenated soyabean oil. 9. A polyamide having the formula:

HHH

a 11 hydrides and acid halides thereof sufllcient to react with the number of amino groups to be amidifled therewith.

11. Process 101' the preparation of polyamides which comprises amidiiying an alkylol polyamine by heating at a 1 temperature between about 120 C. and about 200 C. with approximately a third of a molecular equivalent of coconut oil, and

with an amount of a compound selected from the group consisting of fatty acids containing from 2 to 5 carbon atoms. and the esters, anhydrides and acid halides. thereof suflicient to react with the number 01' amino groups to be amiditied therewith.

EDWIN A. ROBINSON. MAURICE J. KELLEY.

12 nammmcns CITED The following references are of record in the flie 01' this patent: 

